Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
  • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
  • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
  • C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof

Definitions

• the present invention relates to N-sulfomethyl glycinate compounds, a process for the preparation of these compounds and the use of these compounds for the preparation of herbicides of the glyphosate type.
• Glyphosate (N-phosphonomethylglycine) and its salts are wide-spectrum herbicides which are well known in the art. These herbicides and the processes for obtaining them are described, for example, in the following patents: U.S. Pat. No. 3,799,758; U.S. Pat. No. 3,835,000; U.S. Pat. No. 3,868,407; U.S. Pat. No. 3,950,402; U.S. Pat. No. 4,083,893; U.S. Pat. No. 4,147,719 and EP-A-0,019,384. Furthermore, the compound N-sulfomethylglycine is known from U.S. Pat. No. 4,069,048.
• the subject of the invention is to suggest a way of arriving at the glyphosate-type herbicides which has numerous advantages: economy, restricted number of stages, excellent yields and ease of development to the industrial scale.
• the invention relates to a N-sulfomethyl glycinate of formula:
• COOR 1 is a hydrolyzable carboxylic ester group.
• Hydrolyzable groups are well known in the art. Within the scope of the present invention, a hydrolyzable COOR 1 group is understood to mean all the groups which can be lyzed in the presence of water, optionally in an acid or basic medium, to give the corresponding --COOH acid and R 1 OH alcohol.
• a hydrolyzable COOR 1 group is understood to mean a group in which the R 1 radical is in particular chosen from the following radicals:
• radicals being optionally substituted with one or more halogen atoms or C 1 -C 6 alkoxy or alkylthio radicals, the aryl or aralkyl radicals being capable, in addition, of comprising 1 to 4 hetero atoms chosen from the atoms of oxygen, sulfur and nitrogen (for example furyl, thiophenyl or pyridyl).
• R 1 is chosen from the C 1 -C 6 alkyl or C 6 -C 10 aryl or C 7 -C 11 aralkyl groups, the said radicals being optionally substituted with one or more halogen atoms or C 1 -C 6 alkoxy radicals.
• One preparation process consists in putting formaldehyde, sulfur dioxide and a glycinate of formula: H 2 N--CH 2 --COOR 1 in contact.
• the reaction is preferably carried out with the following molar proportions:
• the reaction is generally carried out between 0° and 100° C., preferably between 10° C. and 90° C., by simply mixing the reactants.
• the formaldehyde is used in one or another easily accessible forms. According to the most usual form it is used in the form of an aqueous solution of concentration between 1% and saturation, preferably from 30 to 40%.
• the reaction may be carried out in the presence of an inert solvent; sometimes such a solvent is useless because the reaction medium normally contains water, particularly as a result of the use of formaldehyde in aqueous solution.
• saturated aliphatic hydrocarbons such as n-pentane, isopentane, 2-methylhexane and 2,2,5-trimethylhexane
• aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene
• saturated aliphatic ethers such as tetrahydrofuran and isopentylether
• aromatic ethers such as benzylethyl ether
• saturated aliphatic or aromatic ketones such as methyl ethyl ketone, methylisobutyl ketone and acetophenone
• saturated aliphatic or aromatic halogenated hydrocarbons such as fluorobenzene, 1-chloro-2-methylpropane and isobutyl chloride
• saturated aliphatic or aromatic esters such as isobutyl isobutyrate, ethyl acetate and methyl benzoate
• the saturated aliphatic or aromatic alcohols such as methanol, ethanol, isopropanol and phenol
• saturated aliphatic or aromatic acids such as acetic acid and benzoic acid
• Another particularly advantageous and unexpected preparation process consists in reacting formaldehyde, sulfur dioxide, an alcohol of the formula R OH and glycine of formula H 2 N--CH 2 --COOH.
• the reaction is preferably carried out with the following molar proportions:
• the R 1 OH alcohol will be used as solvent, the other aprotic solvents mentioned above being capable of being used, optionally, as cosolvents.
• ethanol will be chosen as solvent.
• the reaction is, otherwise, carried out in the same conditions as above.
• the subject of the invention is also the use of compounds of formula (I) in the preparation of known herbicides of the glyphosate type, the use consisting in putting the compound of formula (I) in contact with a phosphite of formula:
• a hydrolyzable (R 2 O) 2 P(O) group is understood to mean a group which, under the action of water, optionally in an acid or basic medium, is lyzed to an alcohol R 2 OH and an acid (O)P(OH) 2 .
• a hydrolyzable (R 2 O) 2 P(O) group is understood to mean a group the R 2 radical of which is in particular chosen from the following radicals:
• radicals being optionally substituted with one or more halogen atoms or C 1 -C 6 alkoxy or alkylthio radicals, the aryl or aralkyl radicals being capable, in addition, of comprising 1 to 4 hetero atoms chosen from the atoms of oxygen, sulfur and nitrogen (for example furyl, pyridyl and thiophenyl).
• R 2 is chosen from the C 1 -C 6 alkyl or C 6 -C 10 aryl or C 7 -C 11 aralkyl groups, the said radicals being optionally substituted with one or more halogen atoms or C 1 -C 6 alkoxy radicals.
• the reaction is carried out in the bulk phase or in an inert solvent.
• saturated aliphatic hydrocarbons such as n-pentane, isopentane, 2-methylhexane and 2,2,5-trimethylhexane
• aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene
• saturated aliphatic ethers such as tetrahydrofuran and isopentylether
• aromatic ethers such as benzylethyl ether
• saturated aliphatic or aromatic ketones such as methyl ethyl ketone, methylisobutyl ketone and acetophenone
• saturated aliphatic or aromatic halogenated hydrocarbons such as fluorobenzene, 1-chloro-2-methylpropane and isobutyl chloride
• saturated aliphatic or aromatic esters such as isobutyl isobutyrate, ethyl acetate and methyl benzoate
• the saturated aliphatic or aromatic alcohols such as methanol, isopropanol and phenol
• the saturated aliphatic or aromatic acids such as acetic acid and benzoic acid
• the reaction temperature is between 50° C. and 250° C. or the boiling point of the solvent, and preferably 100° to 200° C.
• the compound of formula (III) is a product which is known from the document EP 0,135,454. It may be hydrolyzed in a known manner to arrive at the N-phosphonomethylglycine or glyphosate herbicide.
• Glycine (7.5 g; 100 millimoles), 95% ethanol (120 cc) and a 31.5% aqueous solution of formaldehyde (19 g; 200 millimoles) are introduced successively into a two-necked flask provided with an alcohol thermometer.
• the suspension obtained is saturated with SO 2 until it has completely dissolved (increase of the temperature to 45° C.).
• ethyl sulfomethylglycinate (18.8 g) is obtained in a purity greater than 95% (determined by NMR at 360 MHz): this is a 95.5% yield with respect to the starting glycine.
• Ethyl sulfomethylglycinate (2.46 g; 12.5 millimoles), xylene (20 cc) and diisopropyl phosphite (2.07 g; 12.5 mmol) are introduced successively into a two-necked flask provided with a thermometer and a means of cooling.
• the suspension is heated for 1 h at 105° C., and after evaporation of the solvent under a vacuum provided by a water-jet pump an orange oil (3.81 g) is recovered, which is shown by titration to contain 40% protected glyphosate.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Soil Working Implements (AREA)

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Citations (7)

• 1988
  • 1988-08-18 FR FR8811141A patent/FR2635522B1/fr not_active Expired - Lifetime
• 1989
  • 1989-08-01 US US07/388,570 patent/US5117043A/en not_active Expired - Fee Related
  • 1989-08-07 CN CN89105602A patent/CN1040362A/zh active Pending
  • 1989-08-10 DE DE8989420302T patent/DE68903455T2/de not_active Expired - Fee Related
  • 1989-08-10 AT AT89420302T patent/ATE82256T1/de not_active IP Right Cessation
  • 1989-08-10 EP EP89420302A patent/EP0356353B1/fr not_active Expired - Lifetime
  • 1989-08-11 KR KR1019890011468A patent/KR900003114A/ko not_active Withdrawn
  • 1989-08-14 TR TR89/0833A patent/TR24158A/xx unknown
  • 1989-08-15 JP JP1210538A patent/JPH02101059A/ja active Pending
  • 1989-08-15 MA MA21865A patent/MA21612A1/fr unknown
  • 1989-08-16 FI FI893866A patent/FI893866A7/fi not_active Application Discontinuation
  • 1989-08-16 PL PL28440689A patent/PL284406A1/xx unknown
  • 1989-08-16 RO RO141304A patent/RO103740B1/ro unknown
  • 1989-08-17 CS CS894851A patent/CS275034B2/cs unknown
  • 1989-08-17 BG BG089562A patent/BG50724A3/xx unknown
  • 1989-08-17 DK DK405389A patent/DK405389A/da not_active Application Discontinuation
  • 1989-08-17 NZ NZ230344A patent/NZ230344A/en unknown
  • 1989-08-17 IL IL91344A patent/IL91344A0/xx unknown
  • 1989-08-17 AU AU40028/89A patent/AU622212B2/en not_active Ceased
  • 1989-08-17 YU YU01613/89A patent/YU161389A/xx unknown
  • 1989-08-17 BG BG095878A patent/BG60104B2/bg unknown
  • 1989-08-17 ZA ZA896293A patent/ZA896293B/xx unknown
  • 1989-08-18 DD DD89331920A patent/DD283992A5/de not_active IP Right Cessation
  • 1989-08-18 PT PT91483A patent/PT91483B/pt not_active IP Right Cessation
  • 1989-08-18 BR BR898904242A patent/BR8904242A/pt unknown
  • 1989-08-18 HU HU894243A patent/HUT51599A/hu unknown
  • 1989-08-18 OA OA59625A patent/OA09426A/xx unknown
• 1992
  • 1992-04-17 CN CN92102843A patent/CN1064868A/zh active Pending
  • 1992-11-20 GR GR920400199T patent/GR3006300T3/el unknown
• 1993
  • 1993-03-11 HK HK216/93A patent/HK21693A/xx unknown

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